WO2021230194A1 - Composition - Google Patents

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Publication number
WO2021230194A1
WO2021230194A1 PCT/JP2021/017684 JP2021017684W WO2021230194A1 WO 2021230194 A1 WO2021230194 A1 WO 2021230194A1 JP 2021017684 W JP2021017684 W JP 2021017684W WO 2021230194 A1 WO2021230194 A1 WO 2021230194A1
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Prior art keywords
polybutadiene
rubber
mass
butadiene
compound
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PCT/JP2021/017684
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English (en)
Japanese (ja)
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恵太 中川
和志 浦山
秀明 高木
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Jsr株式会社
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Publication of WO2021230194A1 publication Critical patent/WO2021230194A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/02—Rubber derivatives containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the present disclosure relates to compositions, and more particularly to compositions containing polybutadiene.
  • Patent Document 1 a method of polymerizing 1,3-butadiene in the presence of a catalyst in an inert solvent such as a hydrocarbon is known (for example, Patent Document 1). , 2).
  • Patent Documents 1 and 2 describe cis 1,4-polymerization of 1,3-butadiene in the presence of 1,2-polybutadiene and a cobalt-based catalyst or nickel-based catalyst, followed by 1 of 1,3-butadiene.
  • 2-It is disclosed that a vinyl cis-polybutadiene rubber is obtained by polymerization.
  • the crosslinked rubber obtained by cross-linking polybutadiene is required to have excellent crack growth resistance and rigidity from the viewpoint of durability and economy. Further, the crosslinked rubber containing carbon black as a reinforcing agent tends to have a larger energy loss (hysteresis loss) at the time of deformation than the rubber containing silica instead of carbon black. On the other hand, as the crosslinked rubber, it is desired that the hysteresis loss is small even when carbon black is blended.
  • the present disclosure has been made in view of the above problems, and the main object of the present invention is to provide a composition capable of obtaining a crosslinked rubber having excellent crack growth resistance and rigidity while maintaining good low hysteresis loss performance. do.
  • compositions are provided in order to solve the above problems.
  • It is composed of (A) polybutadiene obtained by polymerizing 1,3-butadiene in the presence of 1,2-polybutadiene and a lanthanoid-based catalyst, and (B) halogenated isoprene-based rubber and epoxidized diene-based rubber.
  • a composition comprising at least one modified rubber selected from the group.
  • composition of the present disclosure by containing (A) polybutadiene and (B) modified rubber, a crosslinked rubber having excellent crack growth resistance and rigidity can be obtained while maintaining good low hysteresis loss performance. Can be done.
  • composition contains (A) polybutadiene and (B) a modified rubber. Each component will be described in detail below.
  • step Y a lanthanoid-based catalyst
  • step X 2-Polybutadiene and 1,4-Polybutadiene.
  • step X a step of obtaining 1,2-polybutadiene
  • the "rubber component” contained in the composition refers to a polymer capable of obtaining a cured product exhibiting rubber elasticity by thermosetting. This cured product exhibits a property of causing a large deformation (for example, a deformation that expands more than twice when stretched at room temperature) with a small force at room temperature, and rapidly returning to almost the original shape when the force is removed.
  • Crosslinked rubber refers to a cured product obtained by thermally curing a rubber component.
  • Step X is a step of producing 1,2-polybutadiene by polymerizing 1,3-butadiene in the presence of a cobalt-based catalyst.
  • This step X includes a step of preparing a mixture of 1,3-butadiene and an organic solvent, and a step of polymerizing 1,3-butadiene (more specifically, 1,2 polymerization) in the presence of a cobalt-based catalyst. It includes a step of stopping the polymerization reaction.
  • the 1,2-polybutadiene obtained by the polymerization reaction in step X is also referred to as “1,2-polybutadiene (X)”.
  • 1,2 polymerization is the ratio of the monomer unit which the bonding mode of 1,3-butadiene is 1,2 bond in the butadiene polymer produced by the polymerization of 1,3-butadiene. Refers to polymerization in which is more than 50% by mass.
  • the “1,2-polybutadiene” refers to a butadiene polymer in which the proportion of monomer units in which the bonding mode of 1,3-butadiene is 1,2 bonds is more than 50% by mass.
  • the organic solvent used in this step is a solvent containing a hydrocarbon or a halogenated hydrocarbon as a main component.
  • hydrocarbons include saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane and heptane; saturated alicyclic hydrocarbons having 6 to 20 carbon atoms such as cyclopentane and cyclohexane; 1-.
  • Monoolefins such as butene and 2-butene
  • aromatic hydrocarbons such as benzene, toluene and xylene can be mentioned.
  • halogenated hydrocarbon examples include methylene chloride, chloroform, carbon tetrachloride, trichlorethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, brombenzene, chlorotoluene and the like.
  • hydrocarbons can be preferably used as the organic solvent.
  • the phrase "mainly composed of a hydrocarbon or a halogenated hydrocarbon” means that the amount of the hydrocarbon or the halogenated hydrocarbon is more than 50% by mass, preferably 70, based on the total amount of the organic solvent used in this step. It is by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the amount of 1,3-butadiene with respect to the total amount of 1,3-butadiene and the organic solvent is preferably 0.5% by mass or more, preferably 2% by mass or more. Is more preferable.
  • the amount of 1,3-butadiene with respect to the total amount of 1,3-butadiene and the organic solvent is preferably 50% by mass or less, more preferably 30% by mass or less, and 15% by mass or less. Is even more preferable.
  • the temperature at which the mixture of 1,3-butadiene and the organic solvent is prepared is preferably 10 to 50 ° C, more preferably 20 to 40 ° C.
  • the cobalt-based catalyst used contains a cobalt compound.
  • the cobalt compound is preferably a cobalt salt, and specifically, a cobalt halide salt such as cobalt chloride, cobalt bromide, and cobalt iodide; an organic acid cobalt salt such as cobalt octylate, cobalt versatic acid, and cobalt naphthenate. , Etc. can be mentioned. Of these, it is preferable to use an organic acid cobalt salt as the cobalt compound in that it does not contain a halogen atom.
  • the ratio of the cobalt compound used is preferably such that the molar ratio of 1,3-butadiene (1,3-butadiene / Co) to the cobalt atom of the cobalt compound is 5,000 or more.
  • the proportion of the cobalt compound used is preferably such that 1,3-butadiene / Co (molar ratio) is 150,000 or less.
  • 1,3-butadiene / Co (molar ratio) By setting 1,3-butadiene / Co (molar ratio) to 150,000 or less, it is preferable in that a decrease in polymerization activity can be suppressed.
  • the 1,3-butadiene / Co (molar ratio) is more preferably 10,000 or more.
  • the 1,3-butadiene / Co (molar ratio) is more preferably 100,000 or less.
  • the cobalt-based catalyst used in step X preferably further contains a phosphine compound and an organoaluminum compound together with the cobalt compound.
  • the phosphine compound is a phosphine compound having one branched aliphatic hydrocarbon group having 3 or more carbon atoms or an alicyclic hydrocarbon group having 5 or more carbon atoms and two aromatic hydrocarbon groups. Is preferable.
  • the branched aliphatic hydrocarbon group having 3 or more carbon atoms is preferably a branched alkyl group having 3 to 10 carbon atoms.
  • the alicyclic hydrocarbon group having 5 or more carbon atoms is preferably a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms.
  • the aromatic hydrocarbon group is preferably a phenyl group.
  • Preferred specific examples of the phosphine compound include diphenylcyclohexylphosphine, diphenylisopropylphosphine, diphenylisobutylphosphine, diphenylt-butylphosphine, diphenylcyclopentylphosphine, diphenyl (4-methylcyclohexyl) phosphine, diphenylcycloheptylphosphine, diphenylcyclooctylphosphine and the like.
  • the phosphine compound one type can be used alone or two or more types can be used in combination.
  • the blending ratio of the phosphine compound is preferably 1 to 5 mol, more preferably 1.5 to 4 mol, with respect to 1 mol of the cobalt compound.
  • organoaluminum compounds examples include aluminoxane (methylaminoxane and the like) and compounds formed by contacting trialkylaluminum with water (hereinafter referred to as "aluminum hydride compound").
  • aluminoxane one synthesized in advance may be used, or one synthesized in a polymerization system may be used.
  • the contact method between trialkylaluminum and water is such that water is contacted with an inert organic solvent solution of trialkylaluminum in any of steam, liquid and solid (ice) states. good. Further, the contact may be carried out as a dissolved state, a dispersed state or an emulsified state in the inert organic solvent, or as a gas state or a mist state existing in the inert gas.
  • the ratio of the organoaluminum compound used is preferably such that the molar ratio of 1,3-butadiene (1,3-butadiene / Al) to the aluminum atom of the organoaluminum compound is 500 or more. ..
  • 1,3-butadiene / Al (molar ratio) is 500 or more, the reaction easily proceeds sufficiently.
  • the proportion of the organoaluminum compound used is preferably such that 1,3-butadiene / Al is 4,000 or less. When 1,3-butadiene / Al (molar ratio) is 4,000 or less, the polymerization activity tends to be high, which is preferable.
  • the amount of 1,3-butadiene / Al is more preferably 800 or more. Further, 1,3-butadiene / Al is more preferably 2,000 or less.
  • the reaction temperature in 1 and 2 polymerization is usually ⁇ 20 ° C. to 80 ° C., preferably 10 ° C. to 60 ° C.
  • the reaction time is preferably 5 minutes to 6 hours, more preferably 10 to 3 hours.
  • the polymerization reaction may be a batch type or a continuous type.
  • the concentration of 1,3-butadiene in the reaction solution is usually 5 to 80% by mass, preferably 8 to 25% by mass.
  • measures may be taken to suppress the mixing of inactivating compounds such as oxygen, water, or carbon dioxide in the polymerization system.
  • step X it is preferable to terminate the 1,2 polymerization reaction by adding an organoaluminum compound to the polymerization system after the syndiotactic-1, 2 polymerization reaction reaches a desired reaction conversion rate.
  • Examples of the organoaluminum compound used for stopping the polymerization reaction include an alkylaluminum compound and an aluminum hydride compound. Specific examples of these include alkylaluminum compounds such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tripentyl. Examples thereof include aluminum, trihexyl aluminum, tricyclohexyl aluminum, and trioctyl aluminum.
  • the aluminum hydride compound examples include, for example, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, and diisohexyl aluminum hydride. , Dioctyl aluminum hydride, diisooctyl aluminum hydride and the like.
  • the organoaluminum compound used for terminating the 1, 2 polymerization reaction is at least one selected from the group consisting of diisobutylaluminum hydride, triethylaluminum, triisobutylaluminum, and diethylaluminum hydride. preferable.
  • the organoaluminum compound it can be used alone or in combination of two or more.
  • the ratio of the organoaluminum compound used is preferably 1 mol or more, more preferably 5 mol or more, per 1 mol of the cobalt compound used in the 1,2 polymerization reaction.
  • the proportion of the organoaluminum compound used is preferably 20 mol or less, and more preferably 15 mol or less, per 1 mol of the cobalt compound used in the 1,2 polymerization reaction.
  • the temperature at which the polymerization termination reaction is carried out is usually ⁇ 20 ° C. to 80 ° C., preferably 10 ° C. to 60 ° C.
  • the reaction conversion rate in the 1,2 polymerization reaction is preferably 50% or more, more preferably 55% or more, still more preferably 60% or more.
  • 1,2-syndiotactic polybutadiene can be produced as 1,2-polybutadiene (X).
  • the melting point of the obtained 1,2-polybutadiene (X) is preferably 60 ° C. or higher, more preferably 100 ° C. or higher, and even more preferably 120 ° C. or higher.
  • the melting point of 1,2-polybutadiene (X) is preferably 150 ° C. or lower, more preferably 145 ° C. or lower, and even more preferably 140 ° C. or lower.
  • the melting point of 1,2-polybutadiene (X) to 60 ° C. or higher, it is preferable in that the low hysteresis loss performance can be sufficiently increased. Further, it is preferable to set the melting point of 1,2-polybutadiene (X) to 150 ° C. or lower in that the processability of the composition can be improved.
  • the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is preferably 50,000 or more, preferably 70,000 or more. Is more preferable, and 100,000 or more is particularly preferable.
  • the Mw of 1,2-polybutadiene (X) is preferably 500,000 or less, more preferably 400,000 or less, and even more preferably 350,000 or less.
  • the content of 1,2-vinyl bond (1,2-vinyl bond content) in 1,2-polybutadiene (X) is preferably 70% or more, more preferably 80% or more, and 90%. It is more preferably more than that, and even more preferably 95% or more. In particular, when the content of the 1,2-vinyl bond is 90% or more, it is preferable in that the low hysteresis loss performance of the crosslinked rubber obtained by using the present composition can be further improved.
  • the 1,2-vinyl bond content is a value measured using an infrared spectrophotometer.
  • Step Y 1,4-polybutadiene is produced by polymerizing 1,3-butadiene (cis-1,4 polymerization) in the presence of 1,2-polybutadiene and a lanthanoid-based catalyst.
  • 1,2-polybutadiene that is, 1,2-polybutadiene (X)
  • step X 1,2-polybutadiene
  • the production process can be simplified by adding a lanthanide-based catalyst to the reaction solution obtained in the above step X and adding 1,3-butadiene as necessary to polymerize 1,3-butadiene.
  • step Y by adding isoprene at the time of performing cis-1,4 polymerization, isoprene can be polymerized in addition to 1,3-butadiene.
  • 1,4-polybutadiene obtained by the polymerization reaction in step Y is also referred to as "1,4-polybutadiene (Y)".
  • cis-1,4 polymerization means that in the butadiene polymer produced by the polymerization of 1,3-butadiene, the bonding mode of 1,3-butadiene is cis-1,4 bond. Polymerization in which the proportion of monomer units is more than 50% by mass.
  • 1,4-Polybutadiene means that the ratio of the monomer unit in which the bond mode of 1,3-butadiene is 1,4 bond (including cis-1,4 bond and trans-1,4 bond) is 50% by mass.
  • a super butadiene polymer is
  • the lanthanoid catalyst used in step Y contains a lanthanoid compound.
  • a lanthanoid compound is a compound having at least one element belonging to a lanthanoid.
  • the lanthanoid compound may be a reaction product of a compound having a lanthanoid and a Lewis base.
  • the lanthanoid contained in the lanthanoid compound is preferably at least one selected from the group consisting of neodymium, praseodymium, cerium, lanthanum, gadolinium and samarium, and neodymium is particularly preferable.
  • Specific examples of the lanthanoid compound include lanthanoid carboxylates, alcoholides, ⁇ -diketone complexes, phosphates, phosphites and the like.
  • lanthanoid carboxylate examples include the compound represented by the formula (1); "(R 1- CO 2 ) 3 M" (where M is a lanthanoid and R 1 has 1 to 20 carbon atoms. It is a monovalent hydrocarbon group.).
  • R 1 is preferably a saturated or unsaturated monovalent chain hydrocarbon group, and is preferably a linear or branched alkyl group or a cycloalkyl group. Carbonyl group in the formula (1), primary which R 1 has, bonded to secondary or tertiary carbon atom.
  • M neodymium, praseodymium, cerium, lanthanum, gadolinium or samarium are preferable, and neodymium is more preferable.
  • the compound represented by the above formula (1) examples include octanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, and trade name "versatic acid” (manufactured by Shell Chemical Co., Ltd., carboxyl). Examples thereof include salts such as carboxylic acid) whose group is bonded to a tertiary carbon atom. Of these, the compound represented by the above formula (1) is preferably a salt of versatic acid, 2-ethylhexanoic acid or naphthenic acid.
  • alkoxide of lanthanoid has the formula (2); (R 2 O ) compound represented by the 3 M (however, M is a lanthanoid, R 2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms Is mentioned.).
  • R 2 include a monovalent chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
  • R 2 is preferably a monovalent aromatic hydrocarbon group.
  • groups of formula (2) in "R 2 O-" for example, 2-ethyl - hexyl alkoxy group, oleyl alkoxy group, stearyl alkoxy group, a phenoxy group, a benzyl alkoxy group.
  • R 2 O- is 2-ethyl - hexyl alkoxy group, or a benzyl alkoxy group are preferred.
  • the explanation of the above formula (1) is applied to the explanation of M and the preferable example.
  • the ⁇ -diketone complex of the lanthanoid include an acetylacetone complex, a benzoylacetone complex, a propionitrile acetone complex, a valeryl acetone complex, an ethyl acetylacetone complex and the like. Of these, an acetylacetone complex or an ethylacetylacetone complex is preferable.
  • lanthanoid phosphate or phosphite include bis phosphate (2-ethylhexyl) bis phosphate (1-methylheptyl), bis phosphate (p-nonylphenyl), and bis phosphate (polyethylene glycol).
  • the phosphate or phosphite includes bis phosphate (2-ethylhexyl), bis phosphate (1-methylheptyl), 2-ethylhexylphosphonate mono-2-ethylhexyl or bis (2-ethylhexyl). ) Phosphoric acid salts are preferred.
  • the lanthanoid compound used in step Y is preferably a carboxylate or a phosphate, and more preferably a carboxylate.
  • neodymic phosphate or neodymium carboxylate is more preferable, and neodymic versatic acid salt or neodymium 2-ethylhexanoate is particularly preferable.
  • the lanthanoid compound and a Lewis base may be mixed, or the lanthanoid compound and a Lewis base may be reacted to obtain a reaction product.
  • the amount of the Lewis base used is preferably 0 to 30 mol, more preferably 1 to 10 mol, with respect to 1 mol of the lanthanide contained in the lanthanoid compound.
  • Lewis bases include acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, organophosphorus compounds, monovalent or divalent alcohols and the like.
  • one type of lanthanoid compound may be used alone or two or more types may be used in combination.
  • the ratio of the lanthanoid compound used in the step Y is preferably 0.00001 to 1.0 mmol, preferably 0.0001 to 0.5 mmol, based on 100 g of 1,3-butadiene used in the step Y. Is more preferable. It is preferable that the ratio of the lanthanoid compound used is 0.00001 mmol or more because the polymerization activity can be sufficiently increased. Further, by setting the ratio of the lanthanoid compound to 1.0 mmol or less, it is possible to prevent the catalyst concentration from becoming too high, and it is preferable that a decalcification step is not required.
  • the lanthanoid catalyst used in step Y preferably further contains an organoaluminum compound and a halogen compound together with the lanthanoid compound.
  • the organoaluminum compound it is preferable to use at least one selected from the group consisting of aluminoxane, an alkylaluminum compound and an aluminum hydride compound. Among these, it is particularly preferable to use at least one compound selected from the group consisting of an alkylaluminum compound and an aluminum hydride compound (hereinafter referred to as "aluminum compound (L)") in combination with aluminoxane.
  • aluminum compound (L) an aluminum hydride compound
  • aluminoxane used in this step include a compound represented by the following formula (3) and a compound represented by the following formula (4). Also described in Fine Chemicals, 23, (9) 5 (1994), J.Am.Chem.Soc., 115,4971 (1993), and J.Am.Che.Soc., 117,6465 (1995). You may use an aggregate of aluminoxane that is present.
  • R 3 and R 4 are independently monovalent hydrocarbon groups having 1 to 20 carbon atoms, and k and m are independently integers of 2 or more.
  • equation (3) a plurality of R 3 in the case of .m is 2 or more identical groups or different groups from each other, a plurality of R 4 in the formula (4) is the same group or different groups from each other .
  • R 4 in the formula (3) R 3 and the formula in (4) for example a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, t- butyl group, a hexyl group, isohexyl group, octyl Groups, isooctyl groups and the like can be mentioned.
  • a methyl group, an ethyl group, an isobutyl group or a t-butyl group is preferable, and a methyl group is particularly preferable.
  • k and m are preferably integers of 4 to 100.
  • aluminoxane examples include methylaluminoxane (hereinafter also referred to as “MAO”), ethylaluminoxane, n-propylaluminoxane, n-butylaluminoxane, isobutylaluminoxane, t-butylaluminoxane, hexylaluminoxane, isohexylaluminoxane and the like. Can be done. Among these, MAO is preferable.
  • the aluminoxane one type can be used alone or two or more types can be used in combination.
  • the ratio of aluminoxane used shall be such that the amount of aluminum (Al) contained in aluminoxane is 1 to 500 mol with respect to 1 mol of the lanthanoid compound used in the 1,4 polymerization reaction.
  • the amount is preferably 3 to 250 mol, more preferably 5 to 200 mol, and even more preferably 5 to 200 mol.
  • the aluminum compound (L) include the alkylaluminum compound and the hydrided aluminum compound exemplified in the description of the stopping step.
  • the aluminum compound (L) one type may be used alone, or two or more types may be used in combination.
  • the aluminum compound (L) is preferably at least one selected from the group consisting of diisobutylaluminum hydride, triethylaluminum, triisobutylaluminum, and diethylaluminum hydride.
  • the ratio of the aluminum compound (L) to be used is 1 to 700 mol with respect to 1 mol of the lanthanoid compound used in the 1,4 polymerization reaction. It is preferable to use 3 to 500 mol, and more preferably 3 to 500 mol.
  • the halogen compound used as one component of the lanthanoid catalyst is preferably a chlorine-containing compound, and more preferably at least one selected from the group consisting of silicon chloride compounds and hydrocarbon compounds.
  • silicon chloride compound used include trimethylsilyl chloride, triethylsilyl chloride, dimethylsilyl dichloride and the like. Of these, trimethylsilyl chloride can be preferably used as the silicon chloride compound.
  • Specific examples of the chloride hydrocarbon compound include methyl chloride, butyl chloride, hexyl chloride, octyl chloride, chloroform, dichloromethane, benziliden chloride and the like. Of these, it is preferable to use methyl chloride, chloroform or dichloromethane.
  • the ratio of the halogen compound used is such that the molar ratio of the halogen atom (halogen atom / lanthanoid compound) of the halogen compound to 1 mol of the lanthanoid compound is 0.5 to 3.0. Is preferable, 1.0 to 2.5 is more preferable, and 1.2 to 1.8 is even more preferable.
  • the polymerization catalytic activity can be sufficiently increased. Further, by setting the molar ratio to 3.0 or less, the halogen compound can be prevented from becoming a catalytic poison.
  • the reaction temperature at the time of 1,4 polymerization in step Y is preferably ⁇ 30 ° C. to 200 ° C., more preferably 0 ° C. to 150 ° C.
  • the type of the polymerization reaction is not particularly limited, and it may be carried out by using a batch type reactor or by using a multi-stage continuous type reactor or the like.
  • the monomer concentration in the solvent is preferably 5 to 50% by mass, more preferably 7 to 35% by mass. ..
  • the polymerization system has an inactivating action such as oxygen, water or carbon dioxide. It is preferable to take measures to prevent the contamination of compounds.
  • 1,4-polybutadiene having an active terminal can be obtained.
  • the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably 50,000 or more, more preferably 100,000 or more, and 150,000 or more. The above is more preferable.
  • the weight average molecular weight (Mw) of 1,4-polybutadiene (Y) is preferably 2,000,000 or less, more preferably 1,500,000 or less, and 1,000,000 or less. Is more preferable.
  • the weight average molecular weight of 1,4-polybutadiene (Y) is 50,000 or more, the rigidity and wear resistance of the crosslinked rubber tend to be sufficiently high, and when it is 2,000,000 or less, the present composition There is a tendency to ensure sufficient workability.
  • the content of the cis-1,4 structure in 1,4-polybutadiene (Y) is preferably 70% or more, more preferably 80% or more, further preferably 89% or more, 93. % Or more is even more preferable. In particular, when the content of the cis-1,4 structure is 89% or more, it is preferable in that the crack resistance of the crosslinked rubber obtained by using this composition can be improved.
  • the step Y as the (A) polybutadiene, a mixture of 1,4-polybutadiene (Y) and 1,2-polybutadiene (preferably 1,2-syndiotactic polybutadiene) can be obtained.
  • the content ratio of 1,2-polybutadiene is preferably 3% by mass or more with respect to the total amount of 1,2-polybutadiene and 1,4-polybutadiene. It is more preferably 5% by mass or more, and further preferably 10% by mass or more. Further, the content ratio of 1,2-polybutadiene in (A) polybutadiene is preferably 99% by mass or less, preferably 95% by mass or less, based on the total amount of 1,2-polybutadiene and 1,4-polybutadiene. Is more preferable.
  • an antiaging agent for example, 2,4-di-tert-butyl-p-cresol, 4,6-bis (octyl)). Thiomethyl) -o-cresol, etc.
  • an antiaging agent for example, 2,4-di-tert-butyl-p-cresol, 4,6-bis (octyl)). Thiomethyl) -o-cresol, etc.
  • the polymerization terminal of 1,4-polybutadiene having an active terminal may be modified with an alkoxysilane compound. By such a modification reaction, 1,4-polybutadiene having a silicon-containing group derived from an alkoxysilane compound introduced at the polymerization terminal can be obtained.
  • the alkoxysilane compound used in the modification reaction may be any compound that can react with the active terminal, and is not particularly limited.
  • the alkoxysilane compound include epoxy group-containing alkoxysilane compounds such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • An isocyanate group-containing alkoxysilane compound such as 3-isocyanuppropyltrimethoxysilane and 3-isoxapropylmethyldiethoxysilane; 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldi.
  • Carbonyl group-containing alkoxysilane compounds such as ethoxysilane; cyano group-containing alkoxysilane compounds such as 3-cyanopropyltriethoxysilane and 3-cyanopropylmethyldiethoxysilane can be mentioned.
  • (meta) acrylo" means to include "acrylo" and "methacrylo".
  • condensation catalyst When 1,4-polybutadiene is terminal-modified, the compound that undergoes a condensation reaction with the residue of the alkoxysilane compound introduced at the active terminal and is consumed in the desolubilization step after the modification reaction (hereinafter, also referred to as "condensation catalyst"). ) May be further added.
  • the condensation catalyst used is preferably a condensation catalyst containing at least one element among the elements contained in Group 4A, Group 2B, Group 3B, Group 4B and Group 5B of the Periodic Table, for example, tetramethoxytitanium, tetratert-. Examples thereof include butoxytitanium, bis (n-octanoate) tin, tetraethoxyzirconium and the like.
  • polybutadiene containing 1,2-polybutadiene and 1,4-polybutadiene can be obtained.
  • Isolation of polybutadiene can be carried out by a known desolvation method such as steam stripping and a drying operation such as heat treatment.
  • the content of the cis-1,4 bond in the polybutadiene is preferably 1% or more, more preferably 2% or more, and further preferably 5% or more.
  • the content of the cis-1,4 bond in (A) polybutadiene is preferably 95% or less, more preferably 90% or less.
  • the content of cis-1,4 bonds is a value measured using an infrared spectrophotometer.
  • the content of 1 and 2 bonds in (A) polybutadiene is preferably 99% or less, more preferably 98% or less, and even more preferably 95% or less. Further, the content of 1 and 2 bonds in (A) polybutadiene is preferably 5% or more, and more preferably 10% or more. The content of 1 and 2 bonds is a value measured using an infrared spectrophotometer.
  • the Mooney viscosity (ML1 + 4,100 ° C.) of polybutadiene is preferably 10 or more, and more preferably 20 or more. Further, the Mooney viscosity (ML1 + 4,100 ° C.) of (A) polybutadiene is preferably 150 or less, more preferably 100 or less.
  • the Mooney viscosity (ML1 + 4,100 ° C.) of polybutadiene is in the above range, the processability of the present composition can be improved and uniform kneading with various compounding agents can be performed, which is preferable. Is. In this specification, the Mooney viscosity (ML1 + 4,100 ° C.) is a value measured according to JIS K6300-1: 2013.
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in polybutadiene is preferably 1.1 or more, more preferably 2.0 or more, from the viewpoint of ease of production. 2.2 or more is more preferable.
  • the Mw / Mn of (A) polybutadiene is preferably 4.0 or less, more preferably 3.5 or less. When the Mw / Mn of (A) polybutadiene is 4.0 or less, the fracture characteristics of the crosslinked rubber can be further improved.
  • the blending ratio of (A) polybutadiene is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total amount of the rubber component contained in the present composition.
  • the blending ratio of (A) polybutadiene is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, based on the total amount of the rubber component contained in the present composition.
  • the blending ratio of (A) polybutadiene can be appropriately set according to the content ratio of 1,2-polybutadiene and 1,4-polybutadiene in (A) polybutadiene.
  • the content ratio of 1,2-polybutadiene is 1 to 20% by mass and the content ratio of 1,4-polybutadiene is 0.1 to 60% by mass with respect to the total amount of the rubber component contained in the present composition. It is preferable to set the blending ratio of (A) polybutadiene so as to be%.
  • the content ratio of 1,2-polybutadiene is more preferably 2 to 15% by mass, still more preferably 2 to 10% by mass, based on the total amount of the rubber component contained in the present composition.
  • the content of 1,4-polybutadiene is more preferably 0.2 to 50% by mass, still more preferably 0.2 to 40% by mass, based on the total amount of the rubber component contained in the present composition. Is.
  • the modified rubber (B) blended in the present composition is at least one rubber component selected from the group consisting of halogenated isoprene-based rubber and epoxidized diene-based rubber.
  • Halogenated isoprene rubber is a rubber component obtained by halogenating (preferably chlorinating or brominating) a copolymer of isoprene and isoolefin.
  • the isoolefin constituting the main skeleton of the halogenated isoprene rubber preferably has 4 to 6 carbon atoms, and more preferably isobutylene.
  • the content ratio of the structural unit derived from isoolefin is preferably 90.0 to 99.9% by mass, and the content ratio of the structural unit derived from isoprene is preferably 0.1 to 10. It is 0.0% by mass.
  • the halogen content of the halogenated isoprene rubber is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass.
  • the halogenated isoprene rubber is preferably a halogenated isobutylene-isoprene copolymer (hereinafter, also referred to as "halogenated butyl rubber").
  • halogenated butyl rubber chlorinated butyl rubber obtained by reacting an isobutylene-isoprene copolymer with chlorine and brominated butyl rubber obtained by reacting an isobutylene-isoprene copolymer with bromine are preferable.
  • the halogenated isoprene rubber may be a graft copolymer of a halogenated rubber such as chlorinated butyl rubber or brominated butyl rubber and a conjugated diene polymer.
  • the halogenated isoprene rubber preferably has a Mooney viscosity of ML1 + 8 (125 ° C.) of 20 to 60, and more preferably 30 to 60.
  • the Mooney viscosity ML1 + 8 (125 ° C.) is a value measured at a temperature of 125 ° C., where the residual heat time of the L-shaped rotor is 1 minute and the rotation time of the rotor is 8 minutes, in accordance with JIS K-6300-1: 2001. be.
  • halogenated isoprene rubber examples include JSR CHLOROBUTYL1066 and the like as commercial products of chlorinated butyl rubber (Cl-IIR); JSR BROMOBUTYL2222 and JSR BROMOBUTYL2244 as commercial products of brominated butyl rubber (Br-IIR). JSR BROMOBUTYL2255, JSR BROMOBUTYL2266 (all manufactured by JSR Corporation) and the like can be mentioned respectively.
  • epoxidized diene-based rubber examples include, but are not limited to, epoxidized natural rubber (ENR) and epoxidized butadiene rubber (EBR).
  • EMR epoxidized natural rubber
  • EBR epoxidized butadiene rubber
  • the epoxidized diene rubber preferably has an isoprene unit, and the epoxidized natural rubber is more preferable, because it has a high affinity with (A) polybutadiene.
  • the epoxidation rate of the epoxidized diene rubber is preferably 1 mol% or more, more preferably 2 mol% or more, and 5 mol% or more from the viewpoint of sufficiently increasing the rigidity of the crosslinked rubber obtained by using this composition. Is more preferable.
  • the epoxidation rate is preferably 70 mol% or less, more preferably 60 mol% or less, and further preferably 50 mol% or less, from the viewpoint of suppressing deterioration of the crack growth resistance and low hysteresis loss performance of the crosslinked rubber.
  • the epoxidation rate of the epoxidized diene rubber is a value measured by 1 H-NMR.
  • the weight average molecular weight (Mw) of the epoxidized diene rubber is preferably 1,000 or more, more preferably 2,000 or more, from the viewpoint of sufficiently increasing the crack resistance of the crosslinked product. It is more preferably 3,000 or more. Further, from the viewpoint of ensuring the processability of the present composition, the Mw of the epoxidized diene rubber is preferably 200,000 or less, more preferably 100,000 or less, and more preferably 50,000 or less. Is even more preferable.
  • the blending ratio of the modified rubber is preferably 1 part by mass or more with respect to 100 parts by mass of the rubber component contained in the present composition.
  • the blending ratio of the modified rubber (B) is more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more with respect to 100 parts by mass of the rubber component.
  • the blending ratio of (B) the modified rubber is preferably relative to 100 parts by mass of the rubber component contained in the present composition from the viewpoint of maintaining good rigidity and low hysteresis loss performance of the crosslinked rubber. It is 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less.
  • the modified rubber (B) one type may be blended alone, or two or more kinds may be blended together.
  • the present composition contains (A) polybutadiene and (B) modified rubber, but may further contain other components if necessary.
  • the other components can be appropriately selected depending on the intended use of the composition, and examples thereof include inorganic fillers, cross-linking agents, vulcanization accelerators, process oils, and other rubber components.
  • Examples of the inorganic filler include silica and carbon black.
  • Examples of silica include wet silica (hydrous silicic acid), dry silica (silicic anhydride), colloidal silica, precipitated silica, calcium silicate, aluminum silicate and the like. Of these, wet silica is preferable.
  • Examples of carbon black include GPF, FEF, HAF, ISAF, SAF, and the like, but the carbon black is not particularly limited.
  • various reinforcing fillers such as clay and calcium carbonate may be blended in addition to silica and carbon black.
  • the present composition preferably contains at least one filler selected from the group consisting of carbon black and silica as the inorganic filler in that the mechanical properties such as the strength and rigidity of the obtained rubber can be enhanced.
  • the content ratio of the inorganic filler in the present composition is preferably 25 to 130 parts by mass, and more preferably 30 to 110 parts by mass with respect to 100 parts by mass of the total amount of the rubber component contained in the present composition.
  • Cross-linking agent examples include organic peroxides, phenolic resins, sulfur, sulfur compounds, p-quinone, p-quinone dioxime derivatives, bismaleimide compounds, epoxy compounds, silane compounds, amino resins, polyols, polyamines, and triazine compounds. Metal soap and the like can be mentioned.
  • the cross-linking agent is preferably at least one selected from the group consisting of organic peroxides, phenolic resins and sulfur.
  • organic peroxide examples include 1,3-bis (t-butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3,2,5-dimethyl. -2,5-bis (t-butylperoxy) hexene-3,2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,2'-bis (t-butylperoxy) -P-Isopropylbenzene, dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxide and the like can be mentioned.
  • phenol resin examples include a p-substituted phenol-based compound represented by the following general formula (8), an o-substituted phenol / aldehyde condensate, an m-substituted phenol / aldehyde condensate, a brominated alkylphenol / aldehyde condensate, and the like. Can be mentioned. Of these, p-substituted phenolic compounds are preferred.
  • X is a hydroxyl group, an alkyl halide group, or a halogen atom
  • R is a saturated hydrocarbon group having 1 to 15 carbon atoms
  • n is an integer of 0 to 10.
  • the p-substituted phenolic compound can be obtained by a condensation reaction between the p-substituted phenol and an aldehyde (preferably formaldehyde) in the presence of an alkaline catalyst.
  • phenolic resins include the trade name “Tackiroll 201” (alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.) and the trade name “Tackiroll 250-I” (brominated alkylphenol formaldehyde resin with a bromization rate of 4%, Taoka Chemical Industry Co., Ltd.).
  • the amount of the cross-linking agent used is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the total rubber components contained in the present composition. It is more preferably 1 to 10 parts by mass.
  • the amount of the organic peroxide used may be 0.05 to 10 parts by mass with respect to 100 parts by mass of the total rubber components contained in the present composition. It is preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 5 parts by mass.
  • the amount of the organic peroxide used exceeds 10 parts by mass, the degree of cross-linking tends to be excessively high, the moldability is lowered, and the mechanical properties of the obtained cross-linked rubber tend to be lowered.
  • the amount of the organic peroxide used is less than 0.05 parts by mass, the degree of cross-linking is insufficient, and the rubber elasticity and mechanical strength of the obtained cross-linked rubber tend to decrease.
  • the amount of the phenol resin used is preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the total rubber components contained in the present composition. It is more preferably 0.5 to 5 parts by mass.
  • the amount of the phenol resin used exceeds 10 parts by mass, the molding processability tends to decrease.
  • the amount of the phenol resin used is less than 0.2, the degree of cross-linking is insufficient, and the rubber elasticity and mechanical strength of the obtained cross-linked rubber tend to decrease.
  • the amount of sulfur used is preferably 0.1 to 5 parts by mass, preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total rubber components contained in the present composition. It is more preferable to use 3 parts by mass.
  • a cross-linking aid and a cross-linking accelerator together with the cross-linking agent because the cross-linking reaction can be carried out gently and uniform cross-linking can be formed.
  • an organic peroxide is used as the cross-linking agent
  • sulfur, sulfur compounds powdered sulfur, colloidal sulfur, precipitated sulfur, insoluble sulfur, surface-treated sulfur, dipentamethylene thiuram tetrasulfide, etc.
  • oxime compounds are used as cross-linking aids.
  • N, N'-m-phenylene bismaleimide, and divinylbenzene are preferable. These can be used alone or in combination of two or more. Since N, N'-m-phenylene bismaleimide exhibits an action as a cross-linking agent, it can also be used alone as a cross-linking agent.
  • the amount of the cross-linking aid used is preferably 10 parts by mass or less with respect to 100 parts by mass in total of the rubber components contained in the present composition. It is more preferably 2 to 5 parts by mass.
  • the amount of the cross-linking auxiliary used is more than 10 parts by mass, the degree of cross-linking tends to be excessively high, the molding processability is lowered, and the mechanical properties of the obtained cross-linked rubber tend to be lowered.
  • a metal halide strand chloride, ferric chloride, etc.
  • an organic halide chlorinated polypropylene, chloroprene rubber, etc.
  • a metal oxide such as zinc oxide or a dispersant such as stearic acid in addition to the cross-linking accelerator.
  • the vulcanization accelerator is not particularly limited, and examples thereof include sulfenamide-based, guanidine-based, thiuram-based, thiourea-based, thiazole-based, dithiocarbamic acid-based, and xanthate-based compounds.
  • Specific examples of the sulfide accelerator include 2-mercaptobenzothiazole, dibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazylsulfenamide, Nt-butyl-2-benzothiazolesulfenamide, N.
  • the blending amount of the vulcanization accelerator is usually 0.1 to 10 parts by mass, preferably 0.4 to 5 parts by mass with respect to 100 parts by mass of the total amount of the rubber component contained in the present composition. ..
  • the present composition may contain a process oil generally used for oil-expanding a polymer as an oil for oil-expanding.
  • the process oil is blended into the composition, for example, by adding the oil directly during the rubber blending.
  • Preferred process oils include various oils known in the art, such as aromatic oils, paraffin oils, naphthenic oils, vegetable oils, and oils with a low content of polycyclic aromatic compounds (low).
  • PCA oil for example, mild extraction solvate (MES), treated distillate aromatic extract (TDAE), special aromatic extraction from residual oil. Examples include substances (SRAE: special residual aromatic extract) and heavy naphthenic oils.
  • MES MES
  • TDAE Shellex SNR (heavy paraffin obtained by dewaxing distillate oil with a solvent)
  • MES Shellex SNR
  • Vivatec 500 manufactured by H & R Wasag AG
  • SRAE Japan Energy Corp
  • NC140 made by.
  • the blending amount of the process oil is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the total amount of the rubber components contained in the present composition.
  • the present composition may contain a rubber component (other rubber component) different from (A) polybutadiene and (B) modified rubber.
  • the type of such other rubber components is not particularly limited, but for example, styrene butadiene rubber (SBR), natural rubber (NR), isoprene rubber (IR), styrene isoprene copolymer rubber, butadiene isoprene copolymer rubber, modified SBR. , Modified or unmodified polybutadiene obtained by a method not including step Y, and the like.
  • SBR styrene butadiene rubber
  • NR natural rubber
  • IR isoprene rubber
  • styrene isoprene copolymer rubber butadiene isoprene copolymer rubber
  • Modified or unmodified polybutadiene obtained by a method not including step Y, and the like it is preferable that the composition contains at least natural rubber as another rubber component because the effect of improving the
  • the blending ratio of the other rubber components in the present composition is preferably 100 parts by mass with respect to the total amount of the rubber components contained in the present composition, from the viewpoint of obtaining a crosslinked rubber having sufficiently improved crack growth resistance. It is 60 parts by mass or less, more preferably 50 parts by mass or less.
  • the mixing ratio of the other rubber components is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the total amount of the rubber components contained in the present composition.
  • the present composition includes, for example, an antiaging agent, zinc oxide, stearic acid, a softening agent, a silane coupling agent, a compatibilizer, a vulcanization aid, a processing aid, a scorch inhibitor, and a wax.
  • an antiaging agent zinc oxide, stearic acid, a softening agent, a silane coupling agent, a compatibilizer, a vulcanization aid, a processing aid, a scorch inhibitor, and a wax.
  • Various additives generally used in rubber compositions such as, etc. can be blended. These blending ratios can be appropriately selected according to various components as long as the effects of the present disclosure are not impaired.
  • This composition prepared by blending (A) polybutadiene and (B) modified rubber is kneaded using a kneader such as an open kneader (for example, a roll) or a closed kneader (for example, a Banbury mixer). It can be applied to various rubber products as a crosslinked product by being crosslinked (vulcanized) after molding. According to this composition, it is possible to produce a crosslinked body having excellent crack growth resistance while ensuring rigidity.
  • Applications of the bridge include, for example, tire applications such as tire tread, under tread, carcass, sidewall, bead part; sealing material such as packing, gasket, weather strip, O-ring; automobile, ship, aircraft, railway, etc.
  • hoses and hose covers such as diaphragms, rolls, radiator hoses, air hoses; Power transmission belts, etc. Belts; O-rings; Dust boots; Medical equipment materials; Gaskets; Insulation materials for electric wires; Applicable to other industrial products.
  • Q1 1,3-butadiene (for syndiotactic-1,2 polymerization) input amount
  • Q2 1,2-polybutadiene production amount
  • Q3 1,2-unreacted 1,3-butadiene amount in polymerization
  • Q4 1,3- Amount of butadiene (for cis-1,4 polymerization)
  • Q5 1,4-Polybutadiene production amount
  • Q2 Q1 ⁇ (reaction conversion rate of syndiotactic-1 and 2 polymerization) ...
  • Q3 Q1-Q2 ...
  • Q5 (Q3 + Q4) ⁇ (reaction conversion rate of cis-1,4 polymerization) ...
  • 1,3-butadiene was added to the obtained polymer solution.
  • a toluene solution containing 0.045 mmol of trimethylsilyl chloride (Me 3 SiCl) was reacted with 1,3-butadiene 4.5 mmol at 30 ° C. for 60 minutes to prepare the catalyst composition B.
  • This catalyst composition B was put into the above autoclave and reacted at 70 ° C. for 1 hour (cis-1,4 polymerization) to obtain a polymer solution.
  • the reaction conversion rate of the added 1,3-butadiene was almost 100%.
  • This catalyst composition B was put into the above autoclave and reacted at 70 ° C. for 1 hour (cis-1,4 polymerization) to obtain a polymer solution containing polybutadiene.
  • the reaction conversion rate of unreacted 1,3-butadiene in the 1,4 polymerization was about 25%.
  • the content of the -1,4 bond was 5.0%, the content of the 1,2-vinyl bond was 95.0%, and the weight average molecular weight (Mw) was 300,000.
  • the melting point of 1,2-polybutadiene contained in polybutadiene P2 was 121 ° C., and the weight average molecular weight (Mw) was 290,000.
  • Production Example 2 In Production Example 2, the same operations as in Production Example 2 were performed except that the polymerization formulations for the 1st and 2nd polymerizations were as shown in Table 1 below and the polymerization formulations for the cis-1 and 4 polymerizations were as shown in Table 2 below. , Polybutadiene P3 was obtained. The measurement results of each physical property value of the obtained polybutadiene P3 are shown in Table 3 below.
  • a catalyst composition B was prepared by reacting a toluene solution and a toluene solution containing 0.051 mmol of trimethylsilyl chloride (Me 3 SiCl) with 1,3-butadiene 5.1 mmol at 30 ° C. for 60 minutes.
  • This catalyst composition B was put into the above autoclave and reacted at 70 ° C. for 1 hour (cis-1,4 polymerization) to obtain a polymer solution.
  • the reaction conversion rate of the added 1,3-butadiene was almost 100%.
  • CoCL2 Cobalt Chloride
  • PCH Diphenylcyclohexylphosphine
  • AlBuH Diisobutylaluminum hydride
  • NdVer Neodymium versatic acid
  • MeSiCl Trimethylsilyl chloride
  • this rubber composition was vulcanized at 160 ° C. for 12 minutes to obtain a vulcanized rubber. Evaluation of various properties of the obtained vulcanized rubber was performed by the evaluation methods (1) to (3) shown below. The formulation and evaluation results are shown in Table 4 below.
  • a crosslinked rubber sheet having a thickness of 2 mm is formed by molding the obtained rubber composition into a sheet by calendar processing and then vulcanizing it at 160 ° C. for a predetermined time using a vulcanization press machine.
  • a test piece made of the IV type dumbbell described in ASTM D638 was prepared. At this time, the sheet was punched so that the longitudinal direction of the dumbbell was the columnar direction of the sheet, and a crack extending in the anti-columnar direction was formed at the center position of the dumbbell in the longitudinal direction.
  • the obtained test piece was subjected to a constant elongation fatigue test under the conditions of an elongation rate of 100%, a measurement temperature of 23 ° C., and a rotation speed of 300 cpm, and the number of cycles until the test piece broke was measured. It is shown as an index with Comparative Example 1 as 100, and the larger the value, the better the crack resistance.
  • Rigidity (M300) A tensile test was performed using vulcanized rubber as a measurement sample in accordance with JIS K6251: 2010. Using a dumbbell-shaped No. 3 type as a test sample, the tensile stress (M300) at the time of 300% elongation was measured at room temperature.
  • Examples 2 to 5, Comparative Examples 1 to 5 A rubber composition was obtained by kneading in the same manner as in Example 1 except that the compounding formulation was changed to the formulations shown in Tables 4 and 5 below. Further, a vulcanized rubber was produced using the obtained rubber composition in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Tables 4 and 5 below. Regarding the results of each evaluation, Examples 2 and 3 and Comparative Examples 2 and 3 are indicated by an index with Comparative Example 1 as 100, and Comparative Examples 4 and 5 and Comparative Example 5 are 100. It is shown by the index.
  • Silica 2 ULTRASIL VN3 manufactured by Evonik Industries Carbon Black N339: Mitsubishi Chemical Corporation Dia Black N339 Silane coupling agent: Evonik Si69 Sulfide compound: Rhenocure S manufactured by Rheinchemi Anti-aging agent: Nocrack 810NA manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
  • Vulcanization accelerator CZ Noxeller CZ-G manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
  • Vulcanization accelerator D Noxeller D manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd. In the table, "-" indicates that the compound in the corresponding column was not used.
  • Example 4 in which a rubber composition containing (A) polybutadiene and (B) an epoxidized natural rubber as a modified rubber was used, and the polybutadiene component of the rubber composition was made of high cis polybutadiene rubber and syndiotactic 1,2-polybutadiene.
  • the vulture rubber of Example 4 has crack resistance and crack resistance and crack resistance as compared with Comparative Example 4, as compared with Comparative Example 4 in which the epoxidized natural rubber was not blended. In addition to rigidity, low hysteresis loss performance was also excellent.
  • Example 4 The vulcanized rubber of Example 4 was excellent in crack growth resistance, rigidity and low hysteresis loss performance as compared with Comparative Example 5 having the same composition except for the polybutadiene component. Further, Example 5 was also excellent in crack growth resistance, rigidity and low hysteresis loss performance as compared with Comparative Examples 4 and 5.

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Abstract

L'invention concerne une composition contenant: (A) un polybutadiène obtenu par polymérisation d'un 1,3 - butadiène en présence d'un 1, 2 - polybutadiène et d'un catalyseur de type lanthanide; et (B) au moins une sorte de caoutchouc modifié choisi dans le groupe contenant des caoutchoucs de type isoprènes halogénés et des caoutchoucs de type diènes époxydés.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59122531A (ja) * 1982-12-28 1984-07-16 Japan Synthetic Rubber Co Ltd 強度の改良されたゴム組成物
WO2009093695A1 (fr) * 2008-01-23 2009-07-30 Ube Industries, Ltd. Composition de caoutchouc, composition de caoutchouc pour bande de roulement de base, composition de caoutchouc pour toile en caoutchouc, composition de caoutchouc pour flanc de pneu et pneu utilisant les compositions de caoutchouc
JP2016540080A (ja) * 2013-12-03 2016-12-22 株式会社ブリヂストン シス−１，４−ポリブタジエンとシンジオタクチック１，２−ポリブタジエンのブレンドを調製するプロセス
JP2018536758A (ja) * 2015-12-07 2018-12-13 エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ ゴム混合物
JP2019056073A (ja) * 2017-09-22 2019-04-11 宇部興産株式会社 ビニル・シス−ポリブタジエンゴム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59122531A (ja) * 1982-12-28 1984-07-16 Japan Synthetic Rubber Co Ltd 強度の改良されたゴム組成物
WO2009093695A1 (fr) * 2008-01-23 2009-07-30 Ube Industries, Ltd. Composition de caoutchouc, composition de caoutchouc pour bande de roulement de base, composition de caoutchouc pour toile en caoutchouc, composition de caoutchouc pour flanc de pneu et pneu utilisant les compositions de caoutchouc
JP2016540080A (ja) * 2013-12-03 2016-12-22 株式会社ブリヂストン シス−１，４−ポリブタジエンとシンジオタクチック１，２−ポリブタジエンのブレンドを調製するプロセス
JP2018536758A (ja) * 2015-12-07 2018-12-13 エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ ゴム混合物
JP2019056073A (ja) * 2017-09-22 2019-04-11 宇部興産株式会社 ビニル・シス−ポリブタジエンゴム

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